The present invention relates to a method of producing an electrode for a non-aqueous electrolyte battery, and more particularly to a method of producing, with a high productivity, an electrode for a non-aqueous electrolyte battery, which electrode is excellent in mechanical strength.
In accordance with scale reduction and weight reduction of various electronic devices such as OA machines, VTR cameras, portable phones and the like in recent years, there is a demand for higher performance of a secondary battery used in these electronic devices. In order to meet these demands, lithium ion secondary batteries are rapidly being developed for practical use as non-aqueous electrolyte batteries having a high discharge potential and a high discharge capacity.
Each of the positive electrode and the negative electrode of a non-aqueous electrolyte battery is produced by mixing an active material with a binder to form an electrode coating-material (mixture), and applying it onto a collector, followed by drying. The battery is produced by superposing and winding up a positive electrode, a separator and a negative electrode, which are obtained in sheets, and encapsulating them together with an electrolytic solution in a battery container.
However, since a stress is imposed on the electrode at the time of winding up or encapsulating the positive electrode, the separator and the negative electrode, unfavorable peeling of the electrode coating layer is generated if the mechanical strength of the electrode is insufficient. This leads to decrease in the yield, and is a factor for higher costs.
In order to solve this problem, the peeling strength of the electrode coating layer has been conventionally increased by increasing the binder composition in the coating layer. However, increase in the binder composition naturally leads to decrease in the composition of the electrode active material in the electrode coating layer, thereby decreasing the battery capacity per unit weight.
Also, for example, in Japanese Laid-open Patent Publication No. 9-237,623/1997, the adhesiveness of the coating layer is enhanced by allowing the amount of the residual N-methylpyrrolidone (NMP) to be 50 to 500 ppm relative to the electrode weight. According to the examples in said Patent Publication, the amount of the residual NMP is adjusted by increasing the period of time for drying immediately after the application of the electrode coating-material. However, when industrial production is considered, the application and drying must inevitably be carried out in successive steps, so that in order to increase the period of time for drying, the amount of application production per hour must be dropped, or otherwise the drying furnace must be made long and large so as to meet the amount of application production. In either case, the productivity falls.
Further, in Japanese Laid-open Patent Publication No. 7-6,752/1995, the electrodes are heated at a temperature not less than the melting point of the binder after the step of pressing the electrodes so as to prevent non-uniform distribution of the binder for improvement of the peeling strength of the coating layer. However, flexibility of the electrodes is deteriorated if a crystalline polymer material having a melting point is used as the binder. As a result, defective cracks may possibly occur in the electrode coating layer in the case of encapsulating the electrode into a battery container by bending it with a small curvature radius in a square-type battery or the like.
Therefore, the object of the present invention is to solve the above-mentioned problem of the prior art, and to provide a method for industrial and simplified production of an electrode for a non-aqueous electrolyte battery without unfavorable peeling of the electrode coating layer while maintaining the flexibility of the electrode by a method other than a drying treatment immediately after application of the electrode coating-material.
The present inventors have made eager studies and, as a result, found out that an electrode without unfavorable peeling of the coating layer is obtained while maintaining flexibility by using a polymer material substantially having no melting point at not higher than 300xc2x0 C. as the binder, and carrying out a heating treatment under a specific condition after the electrode coating-material is applied and dried with the use of a polymer material substantially having no melting point at no higher than 300xc2x0 C. as the binder, thereby completing the present invention. It is understood that the expressions xe2x80x9chaving no melting point at not higher than 300xc2x0 C.xe2x80x9d and xe2x80x9chaving no melting point at no higher than 300xc2x0 C.xe2x80x9d have the same meaning as xe2x80x9chaving a melting point at or below 300xc2x0 C.xe2x80x9d
That is, the present invention is a method of producing an electrode for a non-aqueous electrolyte battery by mixing an electrode active material with a binder to prepare an electrode coating-material, applying the electrode coating-material onto an electrode collector, drying the electrode having the coating layer formed, and then compression-molding the dried electrode, wherein the method comprises using a polymer material substantially having no melting point at not higher than 300xc2x0 C. as the binder, and carrying out a heating treatment at a temperature not higher than 300xc2x0 C. for less than 30 hours after the electrode coating-material is applied and dried.
In the present invention, it is preferable that the heating treatment is carried out after the electrode is dried, and thereafter the electrode is compression-molded. Further, the electrode is preferably subjected to the heating treatment in a roll state.
The production method of the electrode of the present invention can be applied to any of a positive electrode and a negative electrode.
First, in the method of the present invention, a slurry-like electrode coating-material is prepared by mixing an electrode active material and a binder together with a solvent. Further, in this step, an electrically conductive agent or an additive may possibly be added in accordance with the needs.
As the electrode active material, various materials can be used without particular limitation as long as they are conventionally used as an electrode active material.
As a positive electrode active material, for example, inorganic compounds such as transition metal oxides and transition metal chalcogen compounds containing an alkali metal, conductive polymers such as polyacetylene, poly-p-phenylene, polyphenylenevinylene, polyaniline, polypyrrole, polyazulene, polyphthalocyanine, polythiophene, cross-linked polymers having a disulfide linkage, thionyl chloride and the like may be mentioned. Among these, oxides or chalcogen compounds of transition metals such as cobalt, manganese, molybdenum, vanadium, chromium, iron, copper, titanium and the like are suitable in the case of a secondary battery using a non-aqueous electrolyte solution containing a lithium salt, and LixCoO2 (0 less than xc3x97xe2x89xa61.0), LixNiO2 (0 less than xc3x97xe2x89xa61.0), LixCoyNi1xe2x88x92yO2 (0 less than xc3x97xe2x89xa61.0, 0 less than yxe2x89xa61.0), Li1+xMn2xe2x88x92xO4 (0xe2x89xa6xc3x97xe2x89xa6⅓), Li(M, Mn)2O4 (Mxe2x95x90Cr, Co, Al, B) are especially preferable in view of high potential, stability and long life.
Further, as a negative electrode active material, for example, carbonaceous materials, tin oxides and others are used. The carbonaceous materials are not particularly limited, and for example, amorphous carbon, coal cokes, petroleum cokes, vapor growth carbon fibers, hard carbon (slightly graphitizable carbon), polymer carbon, natural graphite, artificial graphite, and others may be mentioned. Among these, those skilled in the art can make a suitable choice in accordance with the intended properties of the battery. When the material is used in a negative electrode of a secondary battery using a non-aqueous electrolyte solution containing an alkali metal salt, PAN-type carbon fibers, pitch-type carbon fibers and vapor growth carbon fibers are preferable, and particularly PAN-type carbon fibers and pitch-type carbon fibers are preferable because of good doping of lithium ions.
As the binder in the present invention, it is necessary to use a polymer material substantially having no melting point at not higher than 300xc2x0 C. Such a polymer material for use can be various non-crystalline polymer binders that are conventionally used. For example, fluororubbers and the like can be used.
The binder is used usually at an amount of 1 to 40 parts by weight, preferably 1 to 25 parts by weight, especially preferably 1 to 15 parts by weight, with respect to 100 parts by weight of the electrode active material.
The solvent is not particularly limited, and various solvents conventionally used in preparing an electrode coating-material can be used. For example, N-methylpyrrolidone (NMP), methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), cyclohexanone, toluene and others may be mentioned.
The electrically conductive agent can be added for the purpose of complementing the electrically conductive property of the electrode active material in accordance with the needs. The electrically conductive agent is not particularly limited, and various known electrically conductive agents may be suitably used. For example, acetylene black, graphite, fine particles of gold, silver, copper and the like may be mentioned.
In addition, various known additives such as lithium carbonate, oxalic acid, maleic acid and the like can be added.
The electrode active material, the binder, the electrically conductive agent, the solvent and others can be mixed by an ordinary method. For example, they are mixed under a dry air or inert gas atmosphere by a roll mill method.
Next, the obtained slurry-like electrode coating-material is applied onto an electrode collector. The application may be carried out either on both surfaces of the collector or only on one surface in accordance with the object of the electrode. In the case of applying the electrode coating-material on both surfaces of the collector, the subsequent drying step may be carried out after the electrode material is applied simultaneously on both surfaces or alternatively a drying step may be carried out after the electrode coating-material is applied on one surface and subsequently a drying step may be carried out after the coating-material is applied on the other surface.
In the present invention, a metal foil, a metal sheet, a metal net or the like is used as the electrode collector. The metal material for the electrode collector is not particularly limited, and various metal materials that are conventionally used in electrode collectors can be used. As such metal materials, for example, copper, aluminum, stainless steel, nickel, iron, gold, platinum, titanium and the like may be mentioned; and copper, aluminum and the like are preferable. The thickness of the electrode collector to be used is usually 1 to 30 xcexcm, preferably 5 to 20 xcexcm.
The electrode coating-material can be applied on the electrode collector by an ordinary method. For example, the application is carried out with the use of an extrusion coat, a bar coater, a doctor knife, a wire bar or the like.
Subsequently, the electrode having the coating layer formed is dried to remove the solvent. This drying step can be carried out by an ordinary method. For example, it is dried at 110xc2x0 C. for about 6 minutes. If the period of time for drying is too long, it is not preferable because then the productivity of the electrode decreases.
In the production method of the present invention, a heating treatment is carried out at a temperature not higher than 300xc2x0 C. for less than 30 hours after the electrode is dried. By carrying out the heating treatment, a practically sufficient peeling strength is obtained.
The atmosphere for the heating treatment is not particularly limited, but it can be carried out in atmospheric air, in dried air, in an atmosphere of nitrogen gas or rare gas, or in vacuum. The heating treatment is preferably carried out in dried air or in nitrogen gas.
The temperature for the heating treatment is usually within a range of 70 to 300xc2x0 C., preferably within a range of 100 to 300xc2x0 C., more preferably within the range of 130 to 300xc2x0 C. The period of time for the heating treatment is preferably 30 minutes to 24 hours. The higher the temperature for the heating treatment is, the more likely the effect is obtained even with a short period of time for the heating treatment. Those skilled in the art can suitably select the temperature for the heating treatment and the period of time for the heating treatment.
In the present invention, the electrode is cut to predetermined dimensions respectively in the width direction and in the longitudinal direction and compression-molded with the use of a roller press in accordance with the needs, during the period of time after application and drying of the electrode coating-material up till incorporation of the electrode into the battery container. The cutting generally includes a slitting step of forming the electrode to have a predetermined width in the direction of production flow and a cutting step of forming it to have a desired length. By performing the compression-molding, the density of the electrode coating-material is increased, and the electrode is adjusted to have a constant thickness.
In the present invention, the slitting step, the cutting step, the compression-molding step and the heating treatment step may be carried out in any order. Carrying out the heating treatment step before the compression-molding step is generally preferable because then th e residual strain immediately after drying can be eliminated more easily than carrying out the heating treatment step after the compression-molding step.
Further, if the electrode is subjected to the heating treatment before the cutting step, the electrode can be heated as it is wound up in a roll state, thereby providing an advantage that the heating treatment can be carried out in a small heating furnace. Further, if the electrode roll is heated after it is made small by the slitting step, the electrode roll can be handled with easily. Furthermore, in the case of carrying out the heating treatment in a roll state, the effect of the present invention is not affected whether it is an outer circumferential portion or an inner circumferential portion of the roll.
After the electrode is inserted into the battery container, the electrolytic solution is injected into the container, followed by sealing to produce a battery.
The electrolytic solution of a non-aqueous electrolyte battery using the electrode produced by the present invention may be a conventionally known electrolytic solution. As an electrolytic solution of a secondary battery which solution is composed of a non-aqueous electrolytic solution containing an alkali metal salt, propylene carbonate, ethylene carbonate, xcex3-butyrolactone, N-methylpyrrolidone, acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, 1,3-dioxolane, methyl formate, sulfolane, oxazolidone, thionyl chloride, 1,2-dimethoxyethane, diethylene carbonate, derivatives and mixtures thereof and the like may be mentioned. As the electrolyte contained in the electrolytic solution, halides, perchlorates, thiocyanates, boron fluorides, phosphorus fluorides, arsenic fluorides, aluminum fluorides, trifluoromethyl sulfates and the like of an alkali metal, particularly lithium, may be mentioned.
According to the method of producing an electrode for a non-aqueous electrolyte battery of the present invention, an electrode without unfavorable peeling of the coating layer is obtained because using a polymer material substantially having no melting point at not higher than 300xc2x0 C. as a binder, and the heating treatment is carried out at a temperature not higher than 300xc2x0 C. for less than 30 hours after an electrode coating-material is applied and dried on an electrode collector. The reason why the peeling strength is improved by a heating treatment under such a condition is not yet made clear; however, the present inventors consider it as follows.
The thickness of the electrode coating-material immediately after application on the collector and the thickness of the electrode coating layer after evaporation of the solvent by drying are greatly different with a ratio of about 1:xc2xd. Therefore, residual strain may possibly remain in the coating layer during the drying after application. This residual strain may possibly form a site where mechanical strength is locally inferior in the electrode coating layer, and peeling may start at this site where the strength is locally inferior. Therefore, if a heating treatment is carried out after the electrode is dried, the residual strain may possibly be eliminated, and as a result, the site where the mechanical strength is locally inferior may disappear to improve the peeling strength.
Further, according to the production method of the present invention, the flexibility of the electrode is also maintained because a polymer material substantially having no melting point at not higher than 300xc2x0 C. is used as the binder.